CN114335497A - High-performance bismuth-carbon negative electrode material and preparation method and application thereof - Google Patents
High-performance bismuth-carbon negative electrode material and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
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Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a high-performance bismuth-carbon negative electrode material as well as a preparation method and application thereof3+As the metal center, 1,3, 5-trimesic acid (H) is used3BTC) as organic ligand, and preparing Bi-MOFs through hydrothermal reaction, and then using Bi-MOFs as precursorAnd performing simple carbonization treatment to obtain the bismuth nanoparticles (Bi @ CF) coated with the carbon film in situ. The Bi nanoparticles are used as an electroactive component and can provide high battery capacity, the in-situ formed carbon film can promote electron transmission and ion diffusion, and can slow down volume expansion of bismuth in the charge and discharge processes, and the synergistic effect between the two can ensure that the cathode material has excellent electrochemical properties, including long cycle life, high reversible capacity, stable rate performance and the like.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a high-performance bismuth-carbon negative electrode material and a preparation method and application thereof.
Background
Lithium ion batteries have been widely used in recent years in people's daily life as a mobile power source with mature technology. Lithium ion batteries are ubiquitous from a variety of portable electronic devices (such as mobile phones, digital cameras, tablet computers, etc.) to emerging hybrid vehicles and smart grids. Over the past few decades, lithium ion battery positive electrode materials have been rapidly developed and many have been commercialized. Compared with the prior art, the development of the lithium ion battery cathode material is slow, and the electrochemical performance needs to be further improved. Currently, research and development of new high-performance anode materials become an urgent task in the field of new energy.
The alloy negative electrode material can perform alloy reaction with lithium in the electrochemical process to provide high lithium storage capacity, thereby arousing the research interest of the majority of researchers. Wherein, bismuth is used as a typical alloy cathode material and has ultrahigh volume specific capacity (3800mAh cm)-3) Moderate working voltage and small voltage hysteresis, and in addition, the storage capacity of bismuth is large and the toxicity is low, so that the bismuth becomes a high-capacity cathode material with great application potential and commercial value. However, the bismuth negative electrode material has problems of poor conductivity, large volume change and the like in the practical application process. Currently, the most common method is to compound bismuth and various carbon substrates to prepare a bismuth/carbon composite material, thereby improving the electrical conductivity and slowing down the volume expansion, thereby prolonging the cycle life of the battery. Metal Organic Frameworks (MOFs) are ideal precursors or templates for preparing high-performance electrode materials due to their various morphologies, large specific surface area and adjustable porosity. For example, a zinc-carbon composite material can be obtained by carbonizing zinc-based MOF (ZIF-8), and then replacing zinc with bismuth, and finally a Bi @ NC (NC: nitrogen-doped carbon material) composite material can be prepared.
Currently, although the preparation of bismuth/carbon cathode materials has made a certain progress, the method still has the disadvantages of multiple synthesis steps, high energy consumption, low cycle capacity and poor rate capability (especially in the preparation of bismuth/carbon cathode materials)Under a high current density condition), etc. For example, most of the preparation methods involve carbonization at temperatures in excess of 500 ℃ and the use of Ar/H2Gases, both of which are detrimental to the large-scale synthesis of bismuth/carbon anode materials; the prepared cathode material has relatively poor electrochemical performance in a lithium ion battery, the cycle frequency is generally not more than 500 times, and the high rate performance is generally not more than 3.0 A.g-1. Therefore, it is necessary to develop a bismuth/carbon negative electrode material having a simple preparation method, mild preparation conditions, and excellent electrochemical properties.
Disclosure of Invention
To overcome the above-mentioned deficiencies of the prior art, it is a primary object of the present invention to provide a high performance bismuth carbon anode material (Bi @ CF).
The second purpose of the invention is to provide a preparation method of the high-performance bismuth carbon anode material (Bi @ CF).
The third purpose of the invention is to provide the application of the high-performance bismuth carbon anode material (Bi @ CF). The Bi @ CF negative electrode material disclosed by the invention has good electrochemical performance, is superior to the existing bismuth-based composite material in both cycle stability and rate capability, and has important application in lithium ion batteries.
The first object of the present invention is achieved by the following technical solutions:
the high-performance bismuth-carbon negative electrode material (Bi @ CF) is obtained by carbonizing a bismuth-metal organic framework (Bi-MOFs), and the Bi @ CF is formed by compounding bismuth nanoparticles and a surface carbon film.
The Bi @ CF of the present invention exhibits good lithium storage properties, including high reversible capacity (at 0.2 and 0.5 Ag)-1Circulating 200 times under the condition, and the capacity is 705 and 538mAh g-1) (ii) a Long cycle life (at 1.0 Ag)-1The capacity is still maintained at 306mAh g after 900 times of circulation under the condition-1) (ii) a High rate capability (at 5.0 Ag)-1Has a capacity of 151mAh g at a high current density-1) These properties are far superior to commercial bismuth powders.
The second object of the present invention is achieved by the following technical solutions:
the preparation method of the high-performance bismuth-carbon negative electrode material comprises the following specific steps: dissolving bismuth metal salt and 1,3, 5-trimesic acid or derivatives thereof in an organic solvent, performing hydrothermal reaction to obtain a bismuth-metal organic framework (Bi-MOFs), and carbonizing the Bi-MOFs to obtain the high-performance bismuth-carbon negative electrode material (Bi @ CF).
Preferably, the bismuth metal salt comprises bismuth nitrate pentahydrate.
The invention utilizes Bi3+As the metal center, 1,3, 5-trimesic acid (H) is used3BTC) is used as an organic ligand, Bi-MOFs is prepared through hydrothermal reaction, then Bi-MOFs is used as a precursor, and bismuth nanoparticles (Bi @ CF) coated in situ by a carbon film are obtained through simple carbonization treatment, wherein the Bi nanoparticles are used as an electroactive component and can provide high battery capacity, the carbon film formed in situ can promote electron transmission and ion diffusion and can slow down volume expansion of bismuth in the charging and discharging process, and the synergistic effect between the Bi nanoparticles and the bismuth can ensure that the cathode material has excellent electrochemical properties including long cycle life, high reversible capacity, stable rate performance and the like. The Bi @ CF can be used as a negative electrode material of a lithium ion battery, compared with the existing preparation method of a bismuth/carbon negative electrode material, the carbonization temperature is lower, and the gas atmosphere is inert gas (Ar, N)2Etc.) under mild conditions to obtain the bismuth-carbon composite material. When the Bi @ CF is used as a negative electrode material of a lithium ion battery, the prepared Bi @ CF has good electrochemical performance, and both the cycle stability and the rate capability are superior to those of the existing bismuth-based composite material, so that the negative electrode material has wide application prospect.
In the present invention, the metal Bi may be replaced by In, Sn, Sb, etc., and the carbonization treatment can obtain corresponding indium, tin, antimony nanoparticles, such as (M @ CF, M ═ In, Sn, Sb, etc.); h3BTC can be partially or completely converted to ligands with other functional groups (i.e., derivatives of 1,3, 5-trimesic acid), such as 2-amino-1, 3, 5-trimesic acid (H)3BTC-NH2) Thus, the carbonization treatment can obtain a nitrogen-doped carbon film, such as (Bi @ N-CF); while simultaneously changing the metal center andorganic ligands, composite materials of nanoparticles and carbon thin films (M @ X-CF, M ═ In, Sn, Sb, etc., X ═ N, S, etc.) can be obtained In various combinations.
Preferably, the mass ratio of the bismuth metal salt to the 1,3, 5-trimesic acid or the derivative thereof is 1 (4-6).
Preferably, the organic solvent includes, but is not limited to, anhydrous methanol.
Preferably, the concentration of the bismuth metal salt in the organic solvent is (2-3) mg/mL.
Preferably, the temperature of the hydrothermal reaction is 100-150 ℃, and the time is 12-36 h.
Preferably, the carbonization treatment is performed in an inert gas (e.g., Ar, N)2) The treatment is carried out in the atmosphere, the treatment temperature is 400--1. By adjusting the carbonization process parameters, such as temperature and gas atmosphere, composites of metal oxides and carbon can also be obtained, such as: bi2O3@X-CF；In2O3@X-CF；Sb2O3@X-CF；SnO2@ X-CF, X ═ N, S, and the like.
The third object of the present invention is achieved by the following technical solutions:
the high-performance bismuth carbon negative electrode material is applied to the preparation of lithium ion batteries.
The method skillfully utilizes Bi-MOFs as a precursor material, and synthesizes the bismuth nanoparticles (Bi @ CF) coated in situ by the carbon film through simple carbonization treatment under mild conditions (500 ℃ and Ar gas). Meanwhile, the Bi @ CF is used as a lithium battery negative electrode material, so that excellent electrochemical properties (excellent cycle performance and rate performance) are obtained. In terms of cycle performance, at 0.2 and 0.5A g-1At a current density of 200 cycles, capacities of up to 705 and 538mAh g-1Under high current conditions (1.0A g)-1) The reversible capacity is still maintained at 306mAh g after 900 times of circulation-1. In terms of rate capability, at 5.0A g-1The battery can work normally under the high current density, and 151mAh g is obtained-1The lithium storage capacity of (1). Thus, the prepared Bi @ CF has far-reaching performanceIs far superior to commercial bismuth powder and has important application in lithium ion batteries.
The invention also provides a button cell comprising the high-performance bismuth carbon negative electrode material of claim 1.
The preparation method of the button cell comprises the following steps:
s1, grinding the high-performance bismuth-carbon negative electrode material, the carbon black and the sodium alginate of claim 1 uniformly, adding water to prepare slurry, then uniformly coating the slurry on a copper foil, and drying to obtain an electrode plate;
s2, in the water-free and oxygen-free glove box, the opening of the positive electrode shell of the button cell is upward, the button cell is horizontally placed on the base plate, and the electrode slice in the step S1 is placed in the center of the positive electrode shell; then, electrolyte is dripped to soak the surface of the electrode plate, and a diaphragm is clamped to cover the electrode plate; dropwise adding electrolyte again to wet the surface of the diaphragm, clamping a metal lithium sheet and placing the metal lithium sheet in the center of the diaphragm; and finally, stacking a spring piece, covering the negative electrode shell, and sealing to obtain the button cell.
Preferably, the mass ratio of the high-performance bismuth-carbon negative electrode material to the carbon black to the sodium alginate is 8:1: 1.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a high-performance bismuth carbon negative electrode material (Bi @ CF) prepared from Bi3+As the metal center, 1,3, 5-trimesic acid (H) is used3BTC) as an organic ligand, and carrying out hydrothermal reaction to obtain Bi-MOFs, and then using the Bi-MOFs as a precursor to prepare the Bi-MOFs through simple carbonization treatment.
In a first aspect, the Bi @ CF provided by the invention is obtained by simple carbonization treatment of Bi-MOFs, wherein bismuth nanoparticles are coated by a carbon film in situ, and the Bi nanoparticles are used as an electroactive component and can provide high battery capacity, and the carbon film formed in situ can promote electron transmission and ion diffusion and slow down volume expansion of bismuth in the charging and discharging processes, and the bismuth and the Bi nanoparticles have a synergistic effect, so that the cathode material is ensured to have excellent electrochemical performance. Meanwhile, the carbonization temperature used by the preparation method of Bi @ CF is mild, and the gas atmosphere is inert gases such as Ar gas, so that the preparation method is beneficial to large-scale production; meanwhile, MOFs is selected as a precursor, the shape is uniform, the nano particles obtained after carbonization can be well coated in the carbon film, and the metal center and the organic ligand can be changed, so that the expansibility is strong.
In the second aspect, the carbon bismuth nano-particles Bi @ CF are used as a bismuth-based negative electrode material, and are stirred with conductive carbon black and a binder in a solvent to form uniform slurry, and the uniform slurry is coated on a copper foil, and is dried, pressed into sheets and cut to prepare the electrode sheet. The bismuth-based negative electrode material adopted by the electrode slice has long cycle life, high reversible capacity and good rate capability, and the water system binder is adopted in the slurry stirring process, and the deionized water is used as a solvent, so that the green chemical production concept is embodied.
In a third aspect of the invention, the electrode plate made of Bi @ CF is applied to the preparation of a button cell, and the button cell is made of the electrode plate, a lithium metal sheet, an electrolyte, a diaphragm, a spring piece, and positive and negative electrode shells. The bismuth-based negative electrode material adopted by the button cell can react with lithium to generate reversible electrochemical reaction, so that the button cell is ensured to have excellent electrochemical performance, and the cycle stability and the rate capability of the button cell are superior to those of the existing bismuth-based composite material, thereby indicating that the negative electrode material has wide application prospect.
Drawings
FIG. 1 is an SEM image of Bi-MOFs;
FIG. 2 is an SEM image of Bi @ CF;
FIG. 3 is a TEM image of Bi @ CF;
FIG. 4 is an HRTEM image of Bi @ CF;
FIG. 5 is a mapping diagram of elements of Bi @ CF;
FIG. 6 is an XRD pattern of Bi @ CF;
FIG. 7 is a graph comparing the cycling performance of Bi @ CF and commercial bismuth powder;
FIG. 8 is a graph of long cycle performance and rate performance for Bi @ CF.
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The experimental procedures in the following examples were carried out by conventional methods unless otherwise specified, and the test materials used in the following examples were commercially available by conventional methods unless otherwise specified.
Interpretation of terms:
MOFs (metal-organic frameworks) metal-organic frameworks;
bi (bismuth) bismuth;
CF (carbon film) carbon film;
XRD: x-ray powder diffraction;
TEM: a transmission electron microscope;
SEM: field emission scanning electron microscopy.
Example 1 preparation of bismuth carbon negative electrode Material (Bi @ CF)
The Bi @ CF is obtained by carbonizing a bismuth-metal organic framework (Bi-MOFs), the bismuth carbon negative electrode material is formed by compounding bismuth nanoparticles and a surface carbon film, and the preparation method comprises the following steps:
(1) preparation of Bi-MOFs
Firstly, 150mg of bismuth nitrate pentahydrate and 750mg of 1,3, 5-trimesic acid are added into 60mL of anhydrous methanol under the condition of stirring, then the mixed solution is transferred into a 100mL polytetrafluoroethylene reaction kettle liner, and the polytetrafluoroethylene reaction kettle liner is placed into a hydrothermal reaction kettle and reacts for 24 hours at the temperature of 120 ℃. After the reaction, the product was collected by centrifugation (12000 rpm), washed 3 times with anhydrous methanol, and finally dried overnight under vacuum at 60 ℃ to obtain Bi-MOFs.
(2) Preparation of Bi @ CF
Transferring the prepared Bi-MOFs into a porcelain boat, then putting the porcelain boat into a quartz tube, and passing through a tube furnace at 2 ℃ for min under the atmosphere of argon-1Heating to 500 ℃ at a constant temperature for 3 hours to obtain Bi @ CF.
The results of Scanning Electron Microscope (SEM) observation of the prepared Bi-MOFs and Bi @ CF are shown in FIGS. 1 and 2. Wherein FIG. 1 illustrates that the synthesized Bi-MOF has a rod-like morphology; FIG. 2 illustrates that the Bi @ CF composite material obtained by carbonization maintains the original rod-like morphology well, and a carbon film is formed in situ on the surface after carbonization.
Meanwhile, Transmission Electron Microscope (TEM) and high-magnification transmission electron microscope (HRTEM) observations were made on Bi @ CF, and elemental mapping and X-ray diffraction (XRD) analyses were performed, and the results are shown in fig. 3 to 6. FIG. 3 illustrates that the synthesized Bi @ CF has a rod-like morphology and is covered with a carbon film; the lattice fringes of fig. 4 correspond to different crystal planes of Bi, illustrating the formation of Bi nanoparticles; FIG. 5 illustrates the uniform distribution of Bi, C, O elements in the synthesized Bi @ CF composite; fig. 6 is an XRD pattern, consistent with a standard card of Bi, further illustrating the formation of Bi nanoparticles.
EXAMPLE 2 preparation of electrode sheet
After uniformly grinding Bi @ CF (commercial bismuth powder is adopted as a reference), carbon black (SuperP, Timcal) and sodium alginate (Sigma) which are prepared in example 1 according to the mass ratio of 8:1:1, 100mg of the mixture is added into 0.6mL of deionized water to be prepared into slurry, then the slurry is uniformly coated on a copper foil, the copper foil is placed in a forced air drying oven at 80 ℃ for drying overnight, and finally the electrode plate is prepared by punching.
EXAMPLE 3 preparation of button cell batteries
In a water-free and oxygen-free glove box (the water and oxygen content is less than 0.01PPm), the positive electrode shell of the button cell is opened upwards, the button cell is horizontally placed on a base plate, and the electrode plate prepared in the embodiment 2 is placed in the middle of the positive electrode shell; then, 2-3 drops of electrolyte (prepared by EC (ethylene carbonate), DMC (dimethyl carbonate) and EMC (ethyl methyl carbonate) according to the volume ratio of 1:1:1 and containing 1.0M LiPF (ethylene carbonate) are dripped by a rubber head dropper6(lithium hexafluorophosphate) ], soaking the surface of the electrode slice, clamping a diaphragm (celgard-2400film) and covering the electrode slice; dripping 2-3 drops of electrolyte again to wet the surface of the diaphragm; and then clamping a metal lithium sheet in the center of the diaphragm, stacking a spring piece, covering a negative electrode shell, and sealing to obtain the button cell.
Experimental example 1 electrochemical Performance test
The button cell prepared in example 3 was subjected to electrochemical performance (cycling performance and rate capability) tests using a multichannel cell tester (wuhan blue) using current densities of 0.2, 0.5 and 1.0Ag for cycling performance testing-1(ii) a In the rate performance test, the current density is from 0.1Ag-1Sequentially increased to 0.2, 0.5, 1.0, 2.0 and 5.0Ag-1And then returned to 0.1Ag-1。
As can be seen from FIGS. 7 and 8, the cycle performance was 0.2 and 0.5A g-1At a current density of 200 cycles, capacities of up to 705 and 538mAh g-1Under high current conditions (1.0A g)-1) The reversible capacity is still maintained at 306mAh g after 900 times of circulation-1. In terms of rate capability, at 5.0A g-1The battery can work normally under the high current density, and 151mAh g is obtained-1The lithium storage capacity of (1). Therefore, the Bi @ CF composite material is used as the negative electrode material of the lithium ion battery, and excellent cycle performance and rate capability can be obtained.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.
Claims (10)
1. The high-performance bismuth-carbon negative electrode material is characterized by being obtained by carbonizing a bismuth-metal organic framework, and being formed by compounding bismuth nanoparticles and a surface carbon film.
2. The preparation method of the high-performance bismuth-carbon negative electrode material as claimed in claim 1, wherein the bismuth metal salt and the 1,3, 5-trimesic acid or the derivative thereof are dissolved in an organic solvent, the bismuth-metal organic framework is prepared through hydrothermal reaction, and then the bismuth-metal organic framework is carbonized to obtain the high-performance bismuth-carbon negative electrode material.
3. The method of preparing a high performance bismuth carbon anode material of claim 2, wherein the bismuth metal salt comprises bismuth nitrate pentahydrate.
4. The preparation method of the high-performance bismuth-carbon anode material as claimed in claim 2, wherein the mass ratio of the bismuth metal salt to the 1,3, 5-trimesic acid or the derivative thereof is 1 (4-6).
5. The method for preparing a high-performance bismuth-carbon anode material according to claim 2, wherein the concentration of the bismuth metal salt in the organic solvent is (2-3) mg/mL.
6. The method for preparing the high-performance bismuth-carbon anode material as claimed in claim 2, wherein the hydrothermal reaction is carried out at a temperature of 100 ℃ and 150 ℃ for 12-36 h.
7. The preparation method of the high-performance bismuth-carbon anode material as claimed in claim 2, wherein the carbonization treatment is performed in an inert gas atmosphere, the treatment temperature is 400--1。
8. The application of the high-performance bismuth-carbon negative electrode material of claim 1 in preparing a lithium ion battery.
9. A button cell comprising the high performance bismuth carbon negative electrode material of claim 1.
10. The method for preparing button cell batteries according to claim 9, characterized in that it comprises the following steps:
s1, grinding the high-performance bismuth-carbon negative electrode material, the carbon black and the sodium alginate of claim 1 uniformly, adding water to prepare slurry, then uniformly coating the slurry on a copper foil, and drying to obtain an electrode plate;
s2, in the water-free and oxygen-free glove box, the opening of the positive electrode shell of the button cell is upward, the button cell is horizontally placed on the base plate, and the electrode slice in the step S1 is placed in the center of the positive electrode shell; then, electrolyte is dripped to soak the surface of the electrode plate, and a diaphragm is clamped to cover the electrode plate; dropwise adding electrolyte again to wet the surface of the diaphragm, clamping a metal lithium sheet and placing the metal lithium sheet in the center of the diaphragm; and finally, stacking a spring piece, covering the negative electrode shell, and sealing to obtain the button cell.
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